CN112442023B - Heterocyclic derivative and organic electroluminescent device thereof - Google Patents

Heterocyclic derivative and organic electroluminescent device thereof Download PDF

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CN112442023B
CN112442023B CN202011377608.8A CN202011377608A CN112442023B CN 112442023 B CN112442023 B CN 112442023B CN 202011377608 A CN202011377608 A CN 202011377608A CN 112442023 B CN112442023 B CN 112442023B
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deuterium
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CN112442023A (en
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赵倩
王小会
朱鸫达
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Changchun Hyperions Technology Co Ltd
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Changchun Hyperions Technology Co Ltd
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Priority to US17/535,110 priority patent/US20220173333A1/en
Priority to JP2021192199A priority patent/JP7262138B2/en
Priority to KR1020210167964A priority patent/KR20220077093A/en
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Abstract

The invention provides a heterocyclic derivative and an organic electroluminescent device thereof, and relates to the technical field of organic photoelectric materials. The heterocyclic derivative of the formula I has high electron mobility and good hole blocking performance, so that an organic electroluminescent device obtained by using the heterocyclic derivative as an electron transport region material, particularly a hole blocking material, has low driving voltage and high luminous efficiency. The organic electroluminescent device can also comprise a hole transport region, wherein the hole transport region, especially the luminescent auxiliary layer, contains the triarylamine compound shown in the formula II, and as the electron transport region and the hole transport region in the device can better balance current carriers, the quenching of excitons is reduced, and the recombination probability of the current carriers is improved, the organic electroluminescent device has lower driving voltage and higher luminescent efficiency.

Description

Heterocyclic derivative and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a heterocyclic derivative and an organic electroluminescent device thereof.
Background
The OLED technology refers to a technology in which an organic material emits light under the action of an electric field, and can be classified into a Passive Matrix (PMOLED) and an Active Matrix (AMOLED) according to different driving methods. The OLED is a new generation of flat panel display technology following CRT and LCD, and has the characteristics of wide viewing angle, fast response speed, low power consumption, good shock resistance of solid structure, wide working temperature range, lightness and thinness, flexibility and the like, and is known as a 'dream-like display technology'.
The electroluminescence process of an organic electroluminescent device is an energy transfer process, which converts electric energy into light energy, and in this conversion process, the organic electroluminescent device is regarded as an injection type light emitting diode. A voltage is applied to two ends of the organic electroluminescent device, holes are injected into the hole transport layer from the anode of the device through an electric field generated by the voltage, electrons are injected into the electron transport layer from the cathode of the device, two carriers migrate into the light emitting layer and combine to form excitons, and the exciton radiation transition can emit light.
The organic electroluminescent device has a simple sandwich structure, and an organic functional layer is arranged between an anode and a cathode to form a basic device. The organic functional layer can be a single-layer organic functional layer, a double-layer organic functional layer, a three-layer organic functional layer and a multi-layer organic functional layer, and the organic functional layer can be a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and the like.
From the above, the organic electroluminescent device is a laminated structure composed of functional layers with different properties, and the functions of the functional layers are different and are matched with each other to form an organic whole. Each functional layer corresponds to related functional materials, namely a hole injection material, a hole transport material, an electron blocking material, a luminescent material, a hole blocking material, an electron transport material, an electron injection material and the like. Although the performance of the light-emitting material is very important for the organic electroluminescent device, the performance of the device is improved comprehensively, and not only a high-quality light-emitting material is required, but also a plurality of auxiliary materials with excellent properties, such as a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, an electron transport material, an electron injection material and the like, are required. The improvement of the performance of the auxiliary materials is beneficial to the improvement of the performance of the organic electroluminescent device, so that the research and development of new auxiliary materials are of great significance.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a heterocyclic derivative and an organic electroluminescent device thereof.
The invention provides a heterocyclic derivative which has a structural general formula shown in a formula I,
Figure BDA0002808561250000011
ar is1、Ar2The same or different, are selected from the group shown below,
Figure BDA0002808561250000021
the R is0One of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl,
said X0Selected from O, S, N (R)x)、C(Rx)2In a group of (A), the RxOne selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl,
z is selected from C (R)y) Or N, said RyOne of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl, or two adjacent groups are connected to form a ring;
x is selected from O, S, N (Ar), C (Ar)2、Si(Ar)2Ar is selected from one of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;
m is selected from 0,1, 2,3 or 4, R is the same or different and is selected from deuterium, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, or adjacent two groups are connected to form a ring;
said Lx、LyIndependently selected from a single bond, substituted or unsubstituted alkylene of C1-C30, substituted or unsubstituted cycloalkylene of C3-C30, substituted or unsubstituted arylene of C6-C60 and substituted or unsubstituted heteroarylene of C3-C60;
said L1、L2Independently selected from one of single bond, substituted or unsubstituted arylene of C6-C60 and substituted or unsubstituted heteroarylene of C3-C60.
The invention also provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, wherein the organic layer is positioned between the anode and the cathode, the organic layer comprises an electron transmission area, and the electron transmission area contains the heterocyclic derivative.
Has the advantages that: the heterocyclic derivative shown in the formula I has high electron mobility and good hole blocking performance, can well block holes from entering an electron transport region besides well balancing carriers, and therefore an organic electroluminescent device obtained by using the heterocyclic derivative as a hole blocking layer shows low driving voltage and high luminous efficiency.
In addition, the triarylamine compound in the formula II has higher hole mobility, so that a hole transmission region where the triarylamine compound is used as a light-emitting auxiliary layer and an electron transmission region where the hole blocking layer is arranged can effectively balance carriers, the quenching of excitons is reduced, and the recombination probability of the carriers is improved, so that the device has better photoelectric property.
Drawings
FIG. 1 is a drawing showing Compound 1 of the present invention1H NMR chart; FIG. 2 is a drawing showing a scheme of Compound 22 of the present invention1H NMR chart;
FIG. 3 is a drawing showing a scheme of Compound 51 of the present invention1H NMR chart; FIG. 4 shows a schematic representation of compound 108 of the present invention1H NMR chart.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will fall within the scope of the claims of this application after reading the present invention.
The halogen in the invention comprises fluorine, chlorine, bromine and iodine.
The "unsubstituted" in the "substituted or unsubstituted" in the present invention means that a hydrogen atom on the group is not replaced by any substituent.
The "substituted" in the "substituted or unsubstituted" in the present invention means that at least one hydrogen atom on the group is replaced by a substituent. When a plurality of hydrogens is replaced with a plurality of substituents, the plurality of substituents may be the same or different. The position of the hydrogen substituted by the substituent may be any position. The substituent represented by the above "substitution" includes, but is not limited to, at least one of deuterium, halogen, cyano, nitro, alkyl group having from C1 to C30, cycloalkyl group having from C3 to C30, aryl group having from C6 to C60, heteroaryl group having from C3 to C60, and amino group having from C6 to C60.
The linked ring in the present invention means that two groups are linked to each other by a chemical bond, and in the present invention, the linked ring may be a five-membered ring or a six-membered ring or a fused ring, such as a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a triphenylene ring, a fluorene ring, a quinoline ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, etc., but is not limited thereto.
The alkyl group in the present invention refers to a monovalent group obtained by removing one hydrogen atom from an alkane molecule. The alkyl group includes straight-chain alkyl groups and branched-chain alkyl groups. The number of carbon atoms of the alkyl group is not particularly limited, and is preferably C1 to C60, more preferably C1 to C30, still more preferably C1 to C15, and most preferably C1 to C10. Examples of the alkyl group include, but are not limited to, the groups described below, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like. The chain alkyl group having three or more carbons in the present invention includes isomers thereof, for example, propyl group includes n-propyl group and isopropyl group, tert-butyl group includes n-butyl group, tert-butyl group, isobutyl group, sec-butyl group, and the like.
The cycloalkyl group in the present invention means a monovalent group obtained by removing one hydrogen atom from a cycloalkane molecule. The number of carbon atoms of the cycloalkyl group is not particularly limited, and is preferably C3 to C60, more preferably C3 to C30, still more preferably C3 to C15, and most preferably C3 to C10. Examples of the cycloalkyl group include, but are not limited to, groups as described below, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctane, adamantyl, bornyl, norbornyl, cubic alkyl, and the like.
The aryl group in the present invention refers to a monovalent group obtained by removing a hydrogen atom from the parent nucleus of an aromatic hydrocarbon molecule. The aryl group includes monocyclic aryl groups, polycyclic aryl groups, and fused ring aryl groups. The number of carbon atoms of the aryl group is not particularly limited, but is preferably C6 to C60, more preferably C6 to C30, still more preferably C6 to C18, and most preferably C6 to C14. Examples of the aryl group include, but are not limited to, the groups described below, phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, anthracenyl, benzanthracene, phenanthrenyl, triphenylenyl, pyrenyl, benzopyrenyl, perylenyl, fluoranthenyl, indenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, spirobifluorenyl, benzospirobifluorenyl, dibenzospirobifluorenyl, and the like.
The heteroaryl group in the present invention refers to a monovalent group obtained by removing a hydrogen atom from the parent nucleus of a heterocyclic aromatic hydrocarbon molecule. Heteroatoms in the heteroaryl group include, but are not limited to, the atoms described below, O, S, N, Si, B, P, Se, and the like. The heteroaryl group includes monocyclic heteroaryl groups, polycyclic heteroaryl groups, and fused ring heteroaryl groups. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably C3 to C60, more preferably C3 to C30, still more preferably C3 to C15, and most preferably C3 to C8. Examples of the heteroaryl group include, but are not limited to, a pyridyl group, a pyrazinyl group, a pyridazinyl group, a pyrimidinyl group, a triazinyl group, a quinolyl group, an isoquinolyl group, a quinoxalinyl group, a quinazolinyl group, a phenanthroline group, an oxadiazolyl group, an oxazolyl group, a benzoxazolyl group, a naphthoxazolyl group, a phenanthrooxazolyl group, a thiazolyl group, a benzothiazolyl group, a naphthothiazolyl group, a phenanthrothiazolyl group, an imidazolyl group, a benzimidazolyl group, a naphthoimidazolyl group, a phenanthroimidazolyl group, a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, a dibenzothiophenyl group, a carbazolyl group, a benzocarbazolyl group, an acridinyl group and the like.
The alkenyl group in the present invention means a monovalent group obtained by removing one hydrogen atom from an olefin molecule, and includes a monoalkenyl group, a dienyl group, a polyalkenyl group, and the like. The number of carbon atoms of the alkenyl group is not particularly limited, and is preferably C2 to C60, more preferably C2 to C30, still more preferably C2 to C15, and most preferably C2 to C10. Examples of the alkenyl group include, but are not limited to, the groups described below, vinyl group, butadienyl group, and the like.
The alkynyl refers to a monovalent group obtained by removing one hydrogen atom from an alkyne molecule, and the alkynyl comprises a monoalkynyl group, a dialkynyl group, a polyalkynyl group and the like. The number of carbon atoms of the alkynyl group is not particularly limited, and is preferably C2 to C60, more preferably C2 to C30, still more preferably C2 to C15, and most preferably C2 to C10. Examples of such alkynyl groups include, but are not limited to, the groups described below, ethynyl, butadiynyl, and the like.
The alkylene group in the present invention means a divalent group obtained by removing two hydrogens from an alkane molecule. The number of carbon atoms of the alkylene group is not particularly limited, and is preferably C1 to C60, more preferably C1 to C30, still more preferably C1 to C15, and most preferably C1 to C10. Examples of the alkylene group include, but are not limited to, the groups shown below, methylene, ethylene, and the like.
The cycloalkylene group in the present invention means a divalent group obtained by removing two hydrogens from a cycloalkane molecule. The number of carbon atoms of the alkylene group is not particularly limited, and is preferably C3 to C60, more preferably C3 to C30, still more preferably C3 to C15, and most preferably C3 to C10. Examples of the alkylene group include, but are not limited to, groups shown below, adamantyl, camphanylene, norbornylene and the like.
The arylene group in the present invention refers to a divalent group obtained by removing two hydrogen atoms from a parent nucleus in an aromatic hydrocarbon molecule. The arylene group includes monocyclic arylene, polycyclic arylene, fused ring arylene, or combinations thereof. The number of carbon atoms of the arylene group is not particularly limited, and is preferably C6 to C60, more preferably C6 to C30, still more preferably C6 to C18, and most preferably C6 to C14. Examples of the arylene group include, but are not limited to, a phenylene group, a biphenylene group, a terphenylene group, a quaterphenylene group, a naphthylene group, a phenanthrylene group, an anthracenylene group, a triphenylene group, a pyrenylene group, a fluorenylene group, a benzofluorenylene group, a spirobifluorenylene group, a benzospirobifluorene group and the like. The arylene group of the present invention also includes a divalent group obtained by linking a monocyclic aromatic hydrocarbon and a condensed ring aromatic hydrocarbon through a single bond, and a divalent group obtained by linking a condensed ring aromatic hydrocarbon and a condensed ring aromatic hydrocarbon through a single bond, for example
Figure BDA0002808561250000041
Is a divalent group obtained by connecting benzene and phenanthrene through a single bond, and the like.
The heteroarylene group refers to a divalent group obtained by removing two hydrogen atoms from the parent nucleus of a heterocyclic aromatic hydrocarbon molecule. The heteroatoms include, but are not limited to, the atoms shown below, O, S, N, Si, B, P, Se, and the like. The heteroarylene group includes a monocyclic heteroarylene group, a polycyclic heteroarylene group, a fused ring heteroarylene group, or a combination thereof. The polycyclic heteroarylene group may have only one benzene ring substituted with a heteroatom or may have a plurality of benzene rings substituted with a heteroatom. The number of carbon atoms of the heteroarylene group is not particularly limited, but is preferably C6 to C60, more preferably C6Is C6 to C30, more preferably C3 to C15, most preferably C3 to C8. Examples of the heteroarylene group include, but are not limited to, a pyridylene group, a pyrimidylene group, a pyrazinylene group, a pyridazinylene group, a triazinylene group, a furanylene group, a thiophenylene group, a quinolylene group, an isoquinolylene group, a quinoxalylene group, a quinazolinylene group, a phenanthroline group, a benzofuranylene group, a dibenzofuranylene group, a benzothiophenylene group, a dibenzothiophenylene group, a carbazolyl group, a benzocarbazolyl group and the like, as described below. The heteroarylene group of the present invention also includes a divalent group obtained by bonding a heterocyclic aromatic hydrocarbon to a heterocyclic aromatic hydrocarbon by a single bond, and a divalent group obtained by bonding an aromatic hydrocarbon to a heterocyclic aromatic hydrocarbon by a single bond, for example
Figure BDA0002808561250000051
Is a divalent group obtained by connecting pyridine and benzene through a single bond, and the like.
"C1 to C30" in the "substituted or unsubstituted alkyl group having C1 to C30" represents the number of carbon atoms in the unsubstituted "alkyl group" and does not include the number of carbon atoms in the substituent. "C6 to C60" in the "substituted or unsubstituted aryl group having C6 to C60" represents the number of carbon atoms in the unsubstituted "aryl group" and does not include the number of carbon atoms in the substituent. "C3 to C60" in the "substituted or unsubstituted heteroaryl group having C3 to C60" represents the number of carbon atoms in the unsubstituted "heteroaryl group" and does not include the number of carbon atoms in the substituent. "C6 to C60" in the "substituted or unsubstituted arylene group having C6 to C60" represents the number of carbon atoms in the unsubstituted "arylene group" and does not include the number of carbon atoms in the substituent. "C3 to C60" in the "substituted or unsubstituted C3 to C60 heteroarylene" represents the number of carbon atoms in the unsubstituted "heteroarylene" and does not include the number of carbon atoms in the substituent. And so on.
The invention provides a heterocyclic derivative which has a structural general formula shown in a formula I,
Figure BDA0002808561250000052
ar is1、Ar2The same or different, are selected from the group shown below,
Figure BDA0002808561250000053
the R is0One of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl,
said X0Selected from O, S, N (R)x)、C(Rx)2In a group of (A), the RxOne selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl,
z is selected from C (R)y) Or N, said RyOne of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl, or two adjacent groups are connected to form a ring;
x is selected from O, S, N (Ar), C (Ar)2、Si(Ar)2Ar is selected from one of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;
m is selected from 0,1, 2,3 or 4, R is the same or different and is selected from deuterium, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, or adjacent two groups are connected to form a ring;
said Lx、LyIndependently selected from a single bond, substituted or unsubstituted alkylene of C1-C30, substituted or unsubstituted cycloalkyl of C3-C30, substituted or unsubstituted arylene of C6-C60 and substituted or unsubstituted heteroarylene of C3-C60;
said L1、L2Independently selected from one of single bond, substituted or unsubstituted arylene of C6-C60 and substituted or unsubstituted heteroarylene of C3-C60.
Preferably, said Lx、LyIndependently selected from the group consisting of a single bond, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted camphanylene group, a substituted or unsubstituted norbornane group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted benzofluorenylene group, a substituted or unsubstituted spirobifluorenylene group, a substituted or unsubstituted benzospirobifluorenylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted quinoxalinylene group, One of substituted or unsubstituted quinazolinylene and substituted or unsubstituted phenanthroline ylene;
said L1、L2Independently selected from a single bond or one of the groups shown below,
Figure BDA0002808561250000061
the T is the same or different and is selected from N or C (R)m) Said R ismSelected from hydrogen, deuterium, cyanogenOne of a group, a nitro group, a substituted or unsubstituted alkyl group of C1-C30, a substituted or unsubstituted cycloalkyl group of C3-C30, a substituted or unsubstituted aryl group of C6-C60 and a substituted or unsubstituted heteroaryl group of C3-C60;
y is selected from O, S, N (R)n)、C(Rn)2In a group of (A), the RnOne of hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl, or two adjacent groups are connected to form a ring;
said L0The same or different one selected from single bond, substituted or unsubstituted arylene of C6-C60 and substituted or unsubstituted heteroarylene of C3-C60.
Preferably, Ar is1、Ar2Independently selected from one of the groups shown in the following,
Figure BDA0002808561250000071
Figure BDA0002808561250000081
preferably, said L1、L2Independently selected from a single bond or one of the groups shown below,
Figure BDA0002808561250000082
preferably, the heterocyclic derivative is selected from one of the structures shown below,
Figure BDA0002808561250000091
Figure BDA0002808561250000101
Figure BDA0002808561250000111
Figure BDA0002808561250000121
Figure BDA0002808561250000131
Figure BDA0002808561250000141
Figure BDA0002808561250000151
Figure BDA0002808561250000161
some specific chemical structures of the heterocyclic derivatives of formula I of the present invention are listed above, but the present invention is not limited to these listed chemical structures, and any substituent group as defined above based on the structure of formula I should be included.
Further, the present invention also provides an organic electroluminescent device, comprising an anode, an organic layer, and a cathode, wherein the organic layer is located between the anode and the cathode, the organic layer comprises an electron transport region, and the electron transport region contains the heterocyclic derivative of the present invention.
The electron transport region of the present invention is composed of one or more layers of a hole blocking layer, an electron transport layer, an electron injection layer, or a functional layer having an electron injection/transport property. The hole-blocking layer and/or the electron-transporting layer preferably contain the heterocyclic derivative of the present invention, and the hole-blocking layer most preferably contains the heterocyclic derivative of the present invention.
Preferably, the organic layer further includes a hole transport region, the hole transport region includes a triarylamine compound represented by formula II, and the hole transport region of the present invention is formed of one or more layers of an electron blocking layer, a light emission auxiliary layer, a hole transport layer, a hole injection layer, or a functional layer having a hole injection/transport property. The electron blocking layer, the light-emitting auxiliary layer and/or the hole transporting layer preferably contain the triarylamine compound represented by the formula II of the present invention, and the light-emitting auxiliary layer and/or the hole transporting layer most preferably contain the triarylamine compound represented by the formula II of the present invention.
Figure BDA0002808561250000162
Wherein A, B is independently selected from one of the following substituents:
Figure BDA0002808561250000163
wherein, R isaOne of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or two adjacent groups are connected to form a ring;
the R isbOne of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or two adjacent groups are connected to form a ring;
said LaSelected from single bond, substituted or unsubstituted arylene of C6-C30, substituted or unsubstitutedOne of substituted C3-C30 heteroarylene;
a is selected from 0,1, 2,3 or 4, b is selected from 0,1, 2,3, 4 or 5;
c is selected from one of the following groups:
Figure BDA0002808561250000171
wherein, R is12One selected from methyl, ethyl, propyl, butyl, phenyl, tolyl, biphenyl and naphthyl;
the R is13One selected from deuterium, methyl, ethyl, propyl, butyl, cyclohexyl, adamantyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, acridinyl, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, pyrenyl, indolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl;
said LbOne selected from the group consisting of a single bond, phenylene, deuterophenyl, deuteronaphthyl, tolylene, biphenylene, naphthylene, terphenylene, dibenzofuranylene, fluorenylene, dibenzothiophenylene;
c is selected from 0,1, 2,3, 4 or 5; d is selected from 0,1, 2,3 or 4; e is selected from 0,1, 2,3, 4,5, 6 or 7; f is selected from 0,1, 2,3, 4,5, 6, 7, 8 or 9.
Preferably, C is selected from one of the following groups:
Figure BDA0002808561250000172
Figure BDA0002808561250000181
preferably, said R isaIndependently selected from hydrogen, deuterium, methyl, ethyl, propyl, butylOne of an alkyl group, an adamantyl group, a camphanyl group, a norbornyl group, a phenyl group, a tolyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a triphenylene group, an acridinyl group, a spirobifluorenyl group, a 9, 9-dimethylfluorenyl group, a 9, 9-diphenylfluorenyl group, a 9-phenylcarbazolyl group, a pyrenyl group, an indolyl group, a benzothienyl group, a benzofuranyl group, a dibenzothienyl group, a dibenzofuranyl group, or a ring formed by connecting two adjacent groups;
said LaOne selected from the group consisting of a single bond, phenylene, tolylene, biphenylene, naphthylene, terphenylene, dibenzofuranylene, fluorenylene, dibenzothiophenylene;
the R isbThe same or different groups are selected from one of hydrogen, deuterium, methyl, ethyl, propyl, butyl, adamantyl, camphanyl, norbornyl, phenyl, tolyl, biphenyl and terphenyl, or adjacent groups are connected to form a ring.
Preferably, in the triarylamine compound represented by formula II, at least one of the substituents A, B, C contains deuterium.
Preferably, in the triarylamine compound represented by formula II, at least one of the substituents A, B, C contains an adamantyl group.
Preferably, the groups A, B are independently selected from one of the groups shown below,
Figure BDA0002808561250000191
preferably, the group C is selected from one of the groups shown below,
Figure BDA0002808561250000192
Figure BDA0002808561250000201
preferably, the triarylamine compound shown in the formula II is selected from one of the structures shown in the specification,
Figure BDA0002808561250000202
Figure BDA0002808561250000211
Figure BDA0002808561250000221
Figure BDA0002808561250000231
Figure BDA0002808561250000241
Figure BDA0002808561250000251
some specific chemical structures of the triarylamine compound represented by formula II of the present invention are listed above, but the present invention is not limited to these listed chemical structures, and any group having the substituent as defined above based on the structure represented by formula II should be included.
The organic layer in the organic electroluminescent device of the present invention may include one or more of a hole injection layer, a light emission auxiliary layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. Each functional layer may be formed of a single layer film or a multilayer film, and each layer film may contain one material or a plurality of materials. The film thickness of each functional layer is not particularly limited, but is preferably 0.01nm to 1 μm. Wherein at least one functional layer comprises heterocyclic derivatives shown in formula I, and preferably electron transport regions, namely hole blocking layers, electron transport layers and/or electron injection layers comprise heterocyclic derivatives shown in formula I. The hole transport region, i.e. the electron blocking layer, the luminescence auxiliary layer, the hole transport layer and/or the hole injection layer, preferably contains the triarylamine compound of the formula II according to the invention.
The material of each layer of the thin film in the organic electroluminescent device of the present invention is not particularly limited, and other than the heterocyclic derivative represented by formula I of the present invention or the triarylamine compound represented by formula II of the present invention, those known in the art may be used. The materials in the organic functional layers of the above-mentioned organic electroluminescent device and the electrode materials on both sides of the device are described below:
the anode material is preferably a high work function material for hole injection into the organic layer. Anode materials of the present invention include metals, metal oxides, metal alloys, combinations of metals and oxides, conductive polymers, and the like. The anode material includes, but is not limited to, examples of gold, vanadium, chromium, copper, palladium, nickel, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), zinc oxide, indium oxide, tin oxide, antimony (SnO)2Sb), polypyrrole, etc.
The hole injection material has a function of injecting holes into the organic layer, and includes metal oxides, phthalocyanine compounds, arylamine compounds, polycyano-containing conjugated organic materials, high molecular materials, and the like. Examples of the hole transport material include, but are not limited to, a material described below, molybdenum trioxide (MoO)3) Copper phthalocyanine (CuPc), 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), 4' -tris [ 2-naphthylphenylamino ] amine]Triphenylamine (2T-NATA), 1,4,5,8,9, 11-hexaazabenzonitrile (HAT-CN), (2E,2 'E) -2,2' - (cyclopropane-1, 2, 3-triylidene) tris (2- (perfluorophenyl) -acetonitrile), poly (3, 4-ethylenedioxythiophene)/poly (styrenesulfonic acid) (PEDOT/PSS), and the like.
The hole transport material has the functions of injecting holes and balancing carriers, and comprises aromatic amine compounds, carbazole compounds and the like. Examples of the hole transporting material include, but are not limited to, materials described below, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), N4, N4, N4', N4' -tetrakis ([1,1 '-biphenyl ] -4-yl) - [1,1' -biphenyl ] -4,4 '-diamine, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC), N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), 2,7, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (Spiro-TAD), 4' -tris (carbazol-9-yl) triphenylamine (TCTA), and the like.
The light-emitting auxiliary material has a function of injecting hole-balancing carriers, and may also have a function of blocking electrons. Including aromatic amine compounds, carbazole compounds, and the like. Examples of the hole transport material include, but are not limited to, tris (4-biphenyl) amine (TBA), 4',4 ″ -tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (MTDATA), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC), 2,7, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (Spiro-TAD), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), and the like.
The electron blocking material has a function of blocking electrons in the light emitting layer, and includes aromatic amine compounds and the like. Examples of the electron blocking material include, but are not limited to, 4,4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), and the like, as described below.
The light emitting material has a function of receiving holes and electrons and combining them to emit visible light, and is classified into a red light emitting material, a green light emitting material, and a blue light emitting material according to emission colors. The luminescent material may be a fluorescent material or a phosphorescent material. The light-emitting materials can be used as the light-emitting layer alone, or can be doped into the host material to be used as the light-emitting layer.
The blue light material contains perylene derivatives, styryl amine derivatives, anthracene derivatives, fluorene derivatives, metal complexes, organosilicon, organoboron and the like. Examples of the blue light-emitting material include, but are not limited to, 2,5,8, 11-tetra-tert-butylperylene (TBPe), 4' -bis [4- (diphenylamino) styryl ] biphenyl (BDAVBi), 9- [4- (2- (7- (N, N-diphenylamino) -9, 9-diethylfluoren-2-yl) vinyl) phenyl ] -9-phenyl-fluorene (DPAFVF), 9, 10-bis- (2-naphthyl) Anthracene (AND), bis (4, 6-difluorophenylpyridine-C2, N) picolinyliridium (FIrpic), AND the like, which are described below.
The green material comprises coumarin dye, quinacridone copper derivatives, polycyclic aromatic hydrocarbon, organic silicon compounds, pyrazoloquinoxaline derivatives, amino anthracene derivatives, coronene, imidazolone derivatives, thiophene pyrrole, naphthalimide, metal complexes and the like. Examples of such green materials include, but are not limited to, the materials coumarin 545T, N, N' -Dimethylquinacridone (DMQA), 5, 12-Diphenylnaphthonaphthalene (DPT), iridium tris (2-phenylpyridine) (Ir (ppy)3) And the like.
The red light material comprises DCM series material, metal complex and the like. Examples of the red light material include, but are not limited to, 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), 4- (dicyanomethylene) -2-tert-butyl-6- (1,1,7, 7-tetramethyljulolidin-9-enyl) -4H-pyran (DCJTB), bis (1-phenylisoquinoline) (acetylacetone) iridium (III) (Ir (piq)2(acac)), platinum octaethylporphyrin (PtOEP), and the like.
The hole blocking material has the function of blocking holes in the light emitting layer, and comprises heterocyclic compounds such as imidazole compounds, phenanthroline compounds and the like. Examples of the hole blocking material include, but are not limited to, 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the like, as described below. Preference is given to the heterocyclic derivatives of the formula I according to the invention.
The electron transport material has the functions of injecting electrons and balancing carriers, and comprises heterocyclic compounds such as pyridine derivatives, imidazole derivatives, oxadiazole derivatives, triazole derivatives and phenanthroline derivatives, metal complexes and the like. Examples of the electron transport material include, but are not limited to, a material described below, tris (8-hydroxyquinoline) aluminum (III) (Alq)3) 3,3'- [5' - [3- (3-pyridyl) phenyl](TmPyPB), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (PBD), 3- (biphenyl-4-yl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-Triazole (TAZ), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the like.
Electron injection materialHas an effect of injecting electrons into the organic layer, and includes inorganic salts of alkali metals, oxides of alkali metals, organic salts of alkali metals, fluorides of alkali metals, complexes of alkali metals, and the like. Examples of the electron injecting material include, but are not limited to, the material described below, cesium carbonate (Cs)2CO3) Lithium oxide (Li)2O), potassium acetate (CH)3COOK), lithium fluoride (LiF), lithium 8-hydroxyquinoline (Liq), and the like.
The cathode material is preferably a low work function material to facilitate electron injection into the organic layer. The cathode material of the present invention includes metals, metal alloys, and the like. The cathode includes, but is not limited to, examples described below, aluminum, silver, magnesium, calcium, magnesium-silver alloys, and the like.
The method for preparing each layer of the thin film in the organic electroluminescent device of the present invention is not particularly limited, and vacuum evaporation, sputtering, spin coating, spray coating, screen printing, laser transfer printing, and the like can be used, but is not limited thereto.
The organic electroluminescent device is mainly applied to the technical field of information display, and is widely applied to various information displays in the aspect of information display, such as tablet computers, flat televisions, mobile phones, smart watches, digital cameras, VR, vehicle-mounted systems, wearable equipment and the like.
Synthetic examples
The method for preparing the heterocyclic derivative represented by formula I of the present invention is not particularly limited, and conventional methods well known to those skilled in the art may be employed. For example, carbon-carbon coupling reactions and the like, more specifically Suzuki reactions and the like, can be used, and the heterocyclic derivatives of formula I of the present invention can be prepared by several synthetic routes as shown below.
Route one: lx and Ly are different and simultaneously single bond
Figure BDA0002808561250000281
And a second route: lx and Ly are single bonds at the same time
Figure BDA0002808561250000282
Wherein each Q is the same or different and is selected from F, Cl, Br, I; each K, which is the same or different, is selected from
Figure BDA0002808561250000283
The process for preparing the triarylamine compound represented by formula II of the present invention is not particularly limited, and conventional processes well known to those skilled in the art may be employed. For example, carbon-nitrogen coupling reaction, more specifically, a Buchwald reaction, a Ullmann reaction, and the like can be used.
Raw materials and reagents: the raw materials and reagents used in the invention are all pure reagents. The starting materials and reagents used in the following synthetic examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art.
The instrument comprises the following steps: (1) G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer (waters, uk); (2) a Vario EL cube type organic element analyzer (Elementar corporation, germany); (3) model Bruker-510 nuclear magnetic resonance spectrometer (Bruker, germany).
Synthesis example 1: preparation of Compound 1
Figure BDA0002808561250000284
(1) In N2Tricyclohexylphosphine (0.280g,1.0mmol), tris (dibenzylideneacetone) dipalladium (0.458g,0.5mmol) were added to 2-bromospiro [ fluorene-9, 9' -xanthene ] under an atmosphere](12.3g,30mmol), 4-chlorobenzeneboronic acid (3.91g,25mmol), dioxane (80ml), and sodium carbonate solution (1.25M,40ml) were refluxed overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by distillation under the reduced pressure and separated by a silica gel column using dichloromethane and n-hexane (2:1) as eluent, to obtain 8.42g of compound D1 in 76% yield.
(2) In N2Bis (triphenylphosphine) palladium dichloride under an atmosphere(0.245g,0.35mmol) was added to a mixture of bis-pinacolato diborane (5.33g,21.0mmol), Compound D1(7.79g,17.5mmol), potassium acetate (5.15g,52.5mmol) and tetrahydrofuran (230ml) and reacted under reflux for 4 hours. The reaction solution was cooled to room temperature, the tetrahydrofuran solution was distilled off under reduced pressure, chloroform and distilled water were added and the organic layer was separated, the aqueous layer was extracted with chloroform, the organic layer was dried over anhydrous magnesium sulfate, filtered, the solvent was removed by distillation under reduced pressure and then separated by a silica gel column, and dichloromethane and petroleum ether (3:1) were used as eluents to obtain 7.76g of compound E1 with a yield of 83%.
(3) In N2Tetrakis (triphenylphosphine) palladium (0.162g,0.14mmol) was added to a mixed solution of 1-bromo-3, 5-dichlorobenzene (3.16g,14mmol), compound E1(7.48g,14mmol), sodium carbonate solution (2M,24.5ml), ethanol (25ml) and toluene (250ml) under reflux overnight. The reaction solution was cooled to room temperature, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by distillation under the reduced pressure and separated by a silica gel column, eluting with ethyl acetate and n-hexane (2:1), to give 6.28g of compound F1 in 81% yield.
(4) In N2Under the atmosphere, tris (dibenzylideneacetone) dipalladium (0.366g,0.4mmol), tricyclohexylphosphine (0.224g,0.8mmol) were added to a mixed solution of compound F1(5.54g,10mmol), bis (pinacolato) diborane (5.08g,20mmol), sodium carbonate solution (1.25M,32ml), dioxane (65ml), and refluxed overnight. The reaction solution was cooled to room temperature, extracted with dichloromethane, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by distillation under the reduced pressure and separated by a silica gel column, eluting with dichloromethane and n-hexane (5:2), to obtain 5.38G of compound G1 in 73% yield.
(5) In N21,1' -Bidiphenylphosphinoferrocene palladium dichloride (0.732G,0.1mmol) was added to a mixed solution of compound G1(3.68G,5mmol), 2-chlorobenzoxazole (1.84G,12mmol), potassium phosphate solution (2M,10ml) and toluene (50ml) under an atmosphere, and reacted at reflux for one day. The reaction mixture was cooled to room temperature, extracted with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by distillation under reduced pressure, and then separated by a silica gel column, eluting with dichloromethane and ethanol (3:1), to give 2.84g of a purified productCompound 1, yield 79%. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 718.2256, found: 718.2267. theoretical element content (%) C51H30N2O3: c, 85.22; h, 4.21; n,3.90, measured elemental content (%): c, 85.20; h, 4.27; and N, 3.94.1H NMR(600MHz,CDCl3Ppm) delta 8.28(s,1H), 8.22-8.19 (m,2H),8.07(d,1H),8.02(s,1H), 7.95-7.90 (m,3H), 7.89-7.83 (m,3H), 7.66-7.62 (m,5H), 7.60-7.57 (m,1H), 7.46-7.42 (m,1H), 7.40-7.33 (m,6H), 7.31-7.24 (m,2H), 7.11-7.06 (m,2H), 7.02-6.95 (m, 2H). The above results confirmed that the obtained product was the objective product.
Synthesis example 2: preparation of Compound 6
The 2-chlorobenzoxazole in synthesis example 1 was replaced with equimolar 2-chloro-6-methyl-benzoxazole, and the other procedures were the same to give 2.58g of compound 6. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 746.2569, found: 746.2593. theoretical element content (%) C53H34N2O3: c, 85.23; h, 4.59; n,3.75, measured elemental content (%): c, 85.12; h, 4.76; and N, 3.83.
Synthetic example 3: preparation of Compound 19
Synthesis example 1 was replaced with 2-chlorobenzoxazole by equimolar 6-bromo-2-phenylbenzo [ D ]]Oxazole, the other steps being the same, gave 3.05g of compound 19. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 870.2882, found: 870.2894. theoretical element content (%) C63H38N2O3: c, 86.88; h, 4.40; n,3.22, measured elemental content (%): c, 86.97; h, 4.30; and N, 3.21.
Synthetic example 4: preparation of Compound 22
The 4-chlorobenzeneboronic acid in Synthesis example 1 was replaced with equimolar 3-chlorobenzeneboronic acid and 2-chlorobenzoxazole was replaced with equimolar 2-chlorooxazolo [5,4-C]Pyridine, the other steps being the same, gives 2.59g of compound 22. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 720.2161, found: 720.2180. theoretical element content (%) C49H28N4O3: c, 81.65; h, 3.92; n,7.77, measured elemental content (%): c, 81.74; h, 3.98; and N, 7.63.1H NMR(600MHz,CDCl3,ppm)δ:8.70(s,1H),8.67(s,1H),8.42(d,1H),8.39(d,1H),8.27(t,1H),8.20(d,2H),8.09–8.04(m,2H),8.02(t,1H),7.93(d,1H),7.88–7.85(m,1H),7.78–7.70(m,4H),7.67–7.63(m,2H),7.61–7.56(m,1H),7.47–7.41(m,1H),7.37–7.33(m,2H),7.30–7.25(m,2H),7.14–7.10(m,2H),7.01–6.95(m,2H)。
Synthesis example 5: preparation of Compound 29
The same procedures were repeated except for changing the 4-chlorobenzeneboronic acid in synthetic example 1 to equimolar 4-chloro-4-biphenylboronic acid, to obtain 3.26g of compound 29. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 794.2569, found: 794.2585. theoretical element content (%) C57H34N2O3: c, 86.13; h, 4.31; n,3.52, measured elemental content (%): c, 86.09; h, 4.25; and N, 3.60.
Synthetic example 6: preparation of Compound 37
4-Chlorobenzeneboronic acid in Synthesis example 1 was replaced with equimolar 7-chlorodibenzo [ B, D ]]Furan-3-ylboronic acid, the same other procedures were carried out to give 3.03g of compound 37. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 808.2362, found: 808.2382. theoretical element content (%) C57H32N2O4: c, 84.64; h, 3.99; n,3.46, measured elemental content (%): c, 84.70; h, 3.92; n, 3.43.
Synthetic example 7: preparation of Compound 42
The same procedures were repeated except for changing 4-chlorobenzeneboronic acid in synthetic example 1 to equimolar 3-chloro-5-cyanophenylboronic acid to give 2.53g of compound 42. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 743.2209, found: 743.2237. theoretical element content (%) C52H29N3O3: c, 83.97; h, 3.93; n,5.65, measured elemental content (%): c, 83.94; h, 3.98; and N, 5.70.
Synthesis example 8: preparation of Compound 43
Will be combinedThe same procedures were repeated except for changing the molar amount of 4-chlorobenzeneboronic acid used in example 1 to equimolar (4-chlorophenyl-2, 3,5,6-d4) boronic acid to obtain 2.64g of compound 43. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 722.2507, found: 722.2533. theoretical element content (%) C51H26D4N2O3: c, 84.74; h, 4.74; n,3.88, measured elemental content (%): c, 84.69; h, 4.77; and N, 3.85.
Synthetic example 9: preparation of Compound 51
In N2Bis (triphenylphosphine) palladium dichloride (0.123g,0.175mmol) was added to 2-bromospiro [ fluorene-9, 9' -xanthene under an atmosphere](7.20g,17.5mmol), bis-pinacoldiborane (5.33g,21.0mmol), potassium acetate (4.29g,43.75mmol) and tetrahydrofuran (200ml) were refluxed for 3 hours. The reaction solution was cooled to room temperature, the tetrahydrofuran solution was distilled off under reduced pressure, methylene chloride and distilled water were added and the organic layer was separated, the aqueous layer was extracted with methylene chloride, the organic layer was dried over anhydrous magnesium sulfate, filtered, the solvent was distilled off under reduced pressure and then separated by a silica gel column, and 6.98g of compound E5 was obtained in 87% yield from methylene chloride and petroleum ether as eluents.
Synthesis example 1 starting from step (3), Compound E1 in step (3) was replaced with equimolar Compound E5 and 2-chlorobenzoxazole in step (5) was replaced with equimolar 6-bromo-2-phenylbenzo [ D ]]Oxazole, the other steps being the same, gives 3.50g of compound 51. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 794.2569, found: 794.2597. theoretical element content (%) C57H34N2O3: c, 86.13; h, 4.31; n,3.52, measured elemental content (%): c, 86.02; h, 4.39; and N, 3.48.1H NMR(600MHz,CDCl3,ppm)δ:8.16(s,2H),8.11–8.05(m,7H),7.94(d,1H),7.90(dd,1H),7.80–7.74(m,4H),7.69–7.63(m,3H),7.61–7.57(m,1H),7.46–7.39(m,7H),7.38–7.34(m,2H),7.30–7.26(m,2H),7.12–7.07(m,2H),7.03–6.96(m,2H)。
Synthetic example 10: preparation of Compound 57
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene ] of example 1]By substitution with equimolar amounts of 3-bromospiro [ fluorene-9, 9' -xanthene]The same procedure was repeated except for changing 4-chlorobenzeneboronic acid to equimolar 3' -chloro-3-biphenylboronic acid, to give 3.38g of compound 57. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 794.2569, found: 794.2634. theoretical element content (%) C57H34N2O3: c, 86.13; h, 4.31; n,3.52, measured elemental content (%): c, 86.16; h, 4.27; and N, 3.50.
Synthetic example 11: preparation of Compound 65
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene in example 9]By substitution with equimolar amounts of 3-bromospiro [ fluorene-9, 9' -xanthene]6-bromo-2-phenylbenzo [ D ]]The oxazole was replaced with equimolar 2-chlorobenzoxazole and the other steps were the same to give 2.41g of compound 65. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 642.1943, found: 642.1964. theoretical element content (%) C45H26N2O3: c, 84.10; h, 4.08; n,4.36, measured elemental content (%): c, 84.21; h, 4.19; and N, 4.28.
Synthetic example 12: preparation of Compound 71
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene ] of example 1]By substitution with equimolar amounts of 3-bromospiro [ fluorene-9, 9' -xanthene]The same procedure was repeated except that 4-chlorobenzeneboronic acid was changed to equimolar 6-chloro-2-naphthaleneboronic acid, to give 2.73g of compound 71. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 768.2413, found: 768.2446. theoretical element content (%) C55H32N2O3: c, 85.92; h, 4.20; n,3.64, measured elemental content (%): c, 85.80; h, 4.15; and N, 3.68.
Synthetic example 13: preparation of Compound 77
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene ] of example 1]By conversion to equimolar 2-bromospiro [ benzo [ B ]]Fluorene-11, 9' -xanthene]The same other steps were followed to give 2.69g of Compound 77. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 768.2413, found: 768.2448. theoretical element content (%) C55H32N2O3: c, 85.92; h, 4.20; n,3.64, measured elementContent (%): c, 85.96; h, 4.27; n, 3.73.
Synthesis example 14: preparation of Compound 95
The 2-chlorobenzoxazole in Synthesis example 1 was replaced with equimolar 2-chloro-6-trifluoromethylbenzothiazole, and the other procedures were the same to give 2.88g of compound 95. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 886.1547, found: 886.1565. theoretical element content (%) C53H28F6N2OS2: c, 71.77; h, 3.18; n,3.16, measured elemental content (%): c, 71.61; h, 3.21; and N, 3.09.
Synthetic example 15: preparation of Compound 102
The 4-chlorobenzeneboronic acid in synthesis example 1 was replaced with equimolar 3' -chloro-3-biphenylboronic acid, and 2-chlorobenzoxazole was replaced with equimolar 2-chlorobenzothiazole, and the other procedures were the same, to obtain 2.70g of compound 102. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 826.2113, found: 826.2126. theoretical element content (%) C57H34N2OS2: c, 82.78; h, 4.14; n,3.39, measured elemental content (%): c, 82.91; h, 4.18; and N, 3.30.
Synthetic example 16: preparation of Compound 106
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene ] of example 1]By substitution with equimolar amounts of 3-bromospiro [ fluorene-9, 9' -xanthene]The same procedure was repeated except that 4-chlorobenzeneboronic acid was changed to equimolar (7-chloro-9, 9-dimethyl-9H-fluoren-2-yl) boronic acid and 2-chlorobenzoxazole was changed to equimolar 2-chlorobenzothiazole, to give 2.95g of compound 106. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 866.2426, found: 866.2451. theoretical element content (%) C60H38N2OS2: c, 83.11; h, 4.42; n,3.23, measured elemental content (%): c, 83.10; h, 4.45; and N, 3.28.
Synthetic example 17: preparation of Compound 108
In N2Tetrakis (triphenylphosphine) palladium (0.104G,0.09mmol) was added to compound G2(13.3G,18mmol), 2-chlorobenzothiazole (3.66G,21.6mmol), potassium carbonate (2M,18ml) under an atmosphere,The reaction mixture was refluxed for five hours in a mixed solution of dioxane (60 ml). The reaction solution was cooled to room temperature, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by distillation under the reduced pressure and separated by a silica gel column using chloroform and n-hexane (3:2) as eluent, to obtain 6.16G of compound G2-1 in 46% yield.
In N2Bis (triphenylphosphine) palladium dichloride (0.104G,0.09mmol) was added to a mixed solution of compound G2-1(13.3G,5mmol), 2-chlorobenzoxazole (3.66G,6mmol), sodium carbonate (1.25M,8ml) and dioxane (25ml) under an atmosphere, and reacted for eight hours under reflux. The reaction solution was cooled to room temperature, extracted with dichloromethane, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by distillation under reduced pressure and separated by a silica gel column using dichloromethane and n-hexane (2:1) as eluent, to obtain 3.16g of compound 108 in 86% yield. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 734.2028, found: 734.2046. theoretical element content (%) C51H30N2O2S: c, 83.36; h, 4.11; n,3.81, measured elemental content (%): c, 83.47; h, 4.12; n, 3.79.1H NMR(600MHz,CDCl3,ppm)δ:8.33(s,1H),8.29(s,1H),8.23–8.20(m,2H),8.15–8.10(m,2H),8.09–8.05(m,2H),7.93(d,1H),7.87(dd,1H),7.80–7.77(m,1H),7.74–7.70(m,1H),7.68–7.62(m,4H),7.61–7.56(m,2H),7.52–7.48(m,1H),7.46–7.42(m,1H),7.41–7.33(m,4H),7.30–7.25(m,2H),7.22(dd,1H),7.12(dd,1H),7.01–6.95(m,2H)。
Synthetic example 18: preparation of Compound 153
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene ] of example 1]By substitution with equimolar amounts of 3-bromospiro [ fluorene-9, 9' -thiaanthracene]The same procedure was repeated except for replacing 4-chlorobenzeneboronic acid with equimolar 3-chlorobenzeneboronic acid, to give 2.65g of compound 153. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 734.2028, found: 734.2032. theoretical element content (%) C51H30N2O2S: c, 83.36; h, 4.11; n,3.81, measured elemental content (%): c, 83.22; h, 4.07; and N, 3.71.
Synthetic example 19: preparation of Compound 164
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene ] of example 1]By substitution with equimolar amounts of 3-bromospiro [ fluorene-9, 9' -thiaanthracene]The same procedure was repeated except for changing 4-chlorobenzeneboronic acid to equimolar (7-chloro-9, 9-dimethyl-9H-fluoren-2-yl) boronic acid, to give 3.02g of compound 164. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 850.2654, found: 850.2647. theoretical element content (%) C60H38N2O2S: c, 84.68; h, 4.50; n,3.29, measured elemental content (%): c, 84.59; h, 4.45; and N, 3.26.
Synthesis example 20: preparation of Compound 173
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene ] of example 1]By substitution with equimolar amounts of 3-bromospiro [ fluorene-9, 9' -thiaanthracene]The 2-chlorobenzoxazole was replaced with equimolar 2-chlorobenzothiazole and the other steps were the same, to give 2.56g of compound 173. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 766.1571, found: 766.1585. theoretical element content (%) C51H30N2S3: c, 79.87; h, 3.94; n,3.65, measured elemental content (%): c, 79.68; h, 3.83; and N, 3.75.
Synthetic example 21: preparation of Compound 201
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene ] of example 1]By replacement with equimolar 2 '-bromo-10-phenyl-10H-spiro [ acridine-9, 9' -fluorene]The same other steps were repeated to give 3.33g of compound 201. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 793.2729, found: 793.2815. theoretical element content (%) C57H35N3O2: c, 86.23; h, 4.44; n,5.29, measured elemental content (%): c, 86.32; h, 4.38; and N, 5.20.
Synthetic example 22: preparation of Compound 219
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene in example 9]By replacement with equimolar 2 '-bromo-10-phenyl-10H-spiro [ acridine-9, 9' -fluorene]The same procedure was repeated except that 2-chlorobenzoxazole was replaced with equimolar 2- (4-chlorophenyl) benzothiazole to give 3.14g of compound 219. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 901.2585, found: 901.2607. theory of thingsArgument content (%) C63H39N3S2: c, 83.88; h, 4.36; n,4.66, measured elemental content (%): c, 83.74; h, 4.41; n, 4.74.
Synthetic example 23: preparation of Compound 244
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene in example 9]By substitution into equimolar 9' - [9H]Fluorene compounds]3' -bromo-10, 10-dimethyl-spiro [9(10H) -anthracene]The 2-chlorobenzoxazole was replaced with 5-bromo-1, 2-diphenyl-1H-benzimidazole in equimolar amount, and the other steps were the same to give 3.11g of compound 244. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 970.4035, found: 970.4072. theoretical element content (%) C72H50N4: c, 89.04; h, 5.19; n,5.77, measured elemental content (%): c, 89.18; h, 5.08; and N, 5.72.
Synthetic example 24: preparation of Compound 250
Synthesis of 2-bromospiro [ fluorene-9, 9' -xanthene ] of example 1]By replacement with equimolar amounts of 2-bromo-spiro [ 9H-fluorene-9, 9' - [9H ]]Xanthene]The same procedure was repeated except that 4-chlorobenzeneboronic acid was changed to equimolar 3-chlorobenzeneboronic acid, to obtain 2.88g of compound 201. The purity of the solid is not less than 99.9 percent by HPLC detection. Mass spectrum m/z, theoretical value: 718.2256, found: 718.2291. theoretical element content (%) C51H30N2O3: c, 85.22; h, 4.21; n,3.90, measured elemental content (%): c, 85.33; h, 4.26; and N, 3.80.
The target compounds in synthetic examples 2 to 24 were as follows:
Figure BDA0002808561250000331
Figure BDA0002808561250000341
synthetic example 25: preparation of Compound II-1
Figure BDA0002808561250000342
To a 1L reaction flask, toluene (600mL), a-1(20.00g, 0.06mol), b-1(23.83g, 0.06mol), palladium acetate (0.21g, 0.93mmol), sodium tert-butoxide (11.3g, 0.117mol), and tri-tert-butylphosphine (8mL in toluene) were added in that order under nitrogen. And reacted under reflux for 2 hours. After the reaction is stopped, the mixture is cooled to room temperature, filtered through kieselguhr, the filtrate is concentrated, recrystallized through methanol, filtered through suction and rinsed through methanol to obtain a recrystallized solid, and the intermediate A-1(30.41g, the yield is 78%) is obtained, and the purity of the solid is not less than 99.7% through HPLC (high performance liquid chromatography).
Under nitrogen protection, a 1L reaction flask was charged with toluene solvent (600ml), c-1(5.83g, 36mmol), intermediate A-1(23.39g, 36mmol), and Pd in that order2(dba)3(330mg, 0.36mmol), BINAP (0.67g, 1.08mmol) and sodium tert-butoxide (3.23g, 33.6mmol), were dissolved with stirring and reacted under reflux under nitrogen for 24 hours, after completion of the reaction, the reaction solution was washed with dichloromethane and distilled water and extracted by separation. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed, followed by washing with cyclohexane: separating, purifying and refining ethyl acetate 10:1 by column chromatography as eluent to obtain compound II-1(17.89g, yield 68%), and solid purity ≧ 99.1% by HPLC detection.
Mass spectrum m/z, theoretical value: 730.3396, found: 730.3425. theoretical element content (%) C56H34D5N: c, 92.02; h, 6.07; n, 1.92, measured element content (%): c, 92.02; h, 6.08; n, 1.89.
The following target products were prepared in the same manner as in Synthesis example 25:
compound II-47(17.43g) has a solid purity of 99.2% or higher as determined by HPLC. Mass spectrum m/z: 782.3693 (theoretical value: 782.3678). Theoretical element content (%) C60H34D7N: c, 92.03; h, 6.18; n, 1.79, measured elemental content (%): c, 92.05; h, 6.18; n, 1.78.
Compound II-70(19.18g), with a solid purity of > 99.2% by HPLC. Mass spectrum m/z: 806.3798 (theoretical value: 806.3709). Theoretical element content (%) C62H38D5N: c, 92.27; h, 5.99; n, 1.74, measured elemental content (%): c, 92.29; h, 5.99; n, 1.74.
Compound II-78(19.82g) has a solid purity of 99.6% or higher as determined by HPLC. Mass spectrum m/z: 859.4209 (theoretical value: 859.4178). Theoretical element content (%) C66H53N: c, 92.16; h, 6.21; n, 1.63, measured elemental content (%): c, 92.16; h, 6.28; and N, 1.60.
Compound II-85(18.19g), with a solid purity ≧ 99.7% by HPLC. Mass spectrum m/z: 801.3411 (theoretical value: 801.3396). Theoretical element content (%) C62H43N: c, 92.85; h, 5.40; n, 1.75, measured elemental content (%): c, 92.83; h, 5.40; and N, 1.70.
Compound II-90(20.13g), with a solid purity ≧ 98.8% by HPLC. Mass spectrum m/z: 859.4197 (theoretical value: 859.4178). Theoretical element content (%) C66H53N: c, 92.16; h, 6.21; n, 1.63 measured elemental content (%): c, 92.10; h, 6.20; n, 1.62.
Purity of compound 1-102(18.92g) by HPLC ≧ 99.3%. Mass spectrum m/z: 875.3584 (theoretical value: 875.3552). Theoretical element content (%) C68H45N: c, 93.22; h, 5.18; n, 1.60, measured elemental content (%): c, 93.24; h, 5.15; n, 1.53.
The above target compounds are as follows:
Figure BDA0002808561250000351
device embodiments
Description of organic materials: the organic materials are sublimated, and the purity of the organic materials is over 99.99 percent.
Description of the substrate: the glass substrate was ultrasonically cleaned by 5% glass cleaning solution for 2 times, each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times, each for 10 minutes. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C.
Description of vapor deposition System: the device is prepared by vacuum evaporation system in vacuumThe continuous evaporation preparation is finished under the uninterrupted condition. The materials are respectively arranged in different evaporation source quartz crucibles, and the temperatures of the evaporation sources can be independently controlled. The thermal evaporation rate of the organic material or the doped parent organic material is generally set at 0.1nm/s, and the evaporation rate of the doped material is adjusted according to the doping ratio; the evaporation rate of the electrode metal is 0.4-0.6 nm/s. Placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system should be maintained at 5 x 10 in the film manufacturing process-5And (3) evaporating an organic layer and a metal electrode respectively by replacing a mask plate under Pa, detecting the evaporation speed by using an SQM160 quartz crystal film thickness detector of Inficon, and detecting the film thickness by using a quartz crystal oscillator.
Description of the test System: a joint IVL test system is formed by test software, a computer, a K2400 digital source meter manufactured by Keithley of the United states and a PR788 spectral scanning luminance meter manufactured by Photo Research of the United states to test the driving voltage, the luminous efficiency and the like of the organic electroluminescent device.
Example 1: preparation of organic electroluminescent device 1
HAT-CN is thermally evaporated on the ITO transparent electrode to be used as a hole injection layer, and the evaporation thickness is 10 nm; thermally evaporating NPB in the hole injection layer to form a hole transport layer, wherein the evaporation thickness is 50 nm; GH-1: GH-2: GD (47.5: 47.5: 5) is thermally evaporated on the hole transport layer to form a light emitting layer, wherein the thickness of the vapor deposition is 30 nm; thermally evaporating the compound 1 of the invention on the luminescent layer to be used as a hole blocking layer, wherein the evaporation thickness is 5 nm; thermally evaporating ET-1: Liq-50: 50 on the hole blocking layer to form an electron transport layer, wherein the evaporation thickness is 30 nm; carrying out thermal evaporation on Liq serving as an electron injection layer on the electron transport layer, wherein the evaporation thickness is 1 nm; al is thermally deposited on the electron injection layer as a cathode, and the deposition thickness is 150 nm.
The device structure of the organic electroluminescent device 1 is as follows:
ITO/HAT-CN (10nm)/NPB (50nm)/GH-1: GH-2: GD ═ 47.5:47.5:5(30 nm)/compound 1(5nm)/ET-1: Liq ═ 50:50(30nm)/Liq (1nm)/Al (150 nm).
Examples 2 to 11: preparation of organic electroluminescent devices 2-11
The compound 1 in the hole blocking layer in example 1 was replaced with the compound 6, the compound 19, the compound 22, the compound 29, the compound 37, the compound 57, the compound 77, the compound 173, the compound 219, and the compound 244, respectively, and the same procedure was repeated to obtain organic electroluminescent devices 2 to 11.
Example 12: preparation of organic electroluminescent device 12
HAT-CN is thermally evaporated on the ITO transparent electrode to be used as a hole injection layer, and the evaporation thickness is 10 nm; thermally evaporating NPB in the hole injection layer to form a hole transport layer, wherein the evaporation thickness is 50 nm; thermally evaporating the compound II-21 of the invention on the hole transport layer to be used as a luminescence auxiliary layer, wherein the evaporation thickness is 10 nm; GH-1: GH-2: GD (47.5: 47.5: 5) is thermally evaporated on the light-emitting auxiliary layer to form a light-emitting layer, and the thickness of the light-emitting layer is 30 nm; thermally evaporating the compound 1 of the invention on the luminescent layer to be used as a hole blocking layer, wherein the evaporation thickness is 5 nm; thermally evaporating ET-1: Liq-50: 50 on the hole blocking layer to form an electron transport layer, wherein the evaporation thickness is 30 nm; carrying out thermal evaporation on Liq serving as an electron injection layer on the electron transport layer, wherein the evaporation thickness is 1 nm; al is thermally deposited on the electron injection layer as a cathode, and the deposition thickness is 150 nm.
The device structure of the organic electroluminescent device 1 is as follows:
ITO/HAT-CN (10nm)/NPB (50 nm)/compound II-21(10nm)/GH-1: GH-2: GD ═ 47.5:47.5:5(30 nm)/compound 1(5nm)/ET-1: Liq ═ 50:50(30nm)/Liq (1nm)/Al (150 nm).
Examples 13 to 25: preparation of organic electroluminescent devices 13-25
The compound 1 in the hole blocking layer in example 12 was replaced with the compound 42, the compound 43, the compound 51, the compound 65, the compound 71, the compound 95, the compound 102, the compound 106, the compound 108, the compound 153, the compound 164, the compound 201, and the compound 250, and the compound II-21 in the light-emitting auxiliary layer was replaced with the compound II-102, the compound II-1, the compound II-47, the compound II-70, the compound II-119, the compound II-85, the compound II-77, the compound II-79, the compound II-76, the compound II-159, the compound II-90, the compound II-73, and the compound II-78, respectively, and the other steps were the same, whereby organic electroluminescent devices 13 to 25 were obtained.
Comparative examples 1 to 3: preparation of comparative organic electroluminescent devices 1 to 3
The compound 1 in the hole blocking layer in example 1 was replaced with a compound R-1, a compound R-2, and a compound R-3, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 1 to 3.
Comparative examples 4 to 6: preparation of comparative organic electroluminescent devices 4 to 6
The compound 1 in the hole blocking layer in example 12 was replaced with the compound 1, the compound R-1, and the compound II-1 in the light-emitting auxiliary layer was replaced with the compound HT-1, the compound HT-2, and the compound HT-2, respectively, in the same manner as in the other steps, to obtain comparative organic electroluminescent devices 4 to 6.
Figure BDA0002808561250000361
Figure BDA0002808561250000371
The results of the test of the light emitting characteristics of the organic electroluminescent devices prepared in examples 1 to 25 of the present invention and comparative examples 1 to 6 are shown in table 1.
Table 1 test data of light emitting characteristics of organic electroluminescent device
Figure BDA0002808561250000372
Figure BDA0002808561250000381
As can be seen from Table 1, the devices 1 to 11 have lower driving voltages and higher light emitting efficiencies than the comparative devices 1 to 3. This shows that the heterocyclic derivative of formula I of the present invention has good electron mobility and good hole blocking performance, and can effectively block holes in the light emitting layer, so that electrons and holes can effectively form excitons in the light emitting layer.
Compared with the comparison devices 4-6, the organic light-emitting devices 12-25 are lower in driving voltage and higher in light-emitting efficiency. This shows that the triarylamine compound shown in formula II has high hole mobility, can effectively transport holes, and simultaneously shows that the electron transport region where the hole blocking layer containing the heterocyclic derivative shown in formula I is located and the hole transport region where the light-emitting auxiliary layer containing the triarylamine compound shown in formula II is located have better balance between the injection and the transport of electrons and holes, thereby reducing the quenching of excitons, improving the recombination probability of carriers, and having lower driving voltage and higher light-emitting efficiency.
It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.

Claims (9)

1. A heterocyclic derivative is characterized by having a structural general formula shown as a formula I,
Figure FDA0003144721800000011
ar is1、Ar2The same or different, independently selected from one of the following groups,
Figure FDA0003144721800000012
Figure FDA0003144721800000021
x is selected from O, S, N (Ar), C (Ar)2Ar is selected from one of C1-C10 alkyl and deuterium substituted or unsubstituted C6-C14 aryl;
m is selected from 0,1, 2,3 or 4, R is the same or different and is selected from deuterium, alkyl of C1-C10, cycloalkyl of C3-C10, deuterium substituted or unsubstituted aryl of C6-C14, or adjacent two groups are connected to form a benzene ring;
said Lx、LyIndependently selected from a single bond, substituted or unsubstituted arylene of C6-C14 and substituted or unsubstituted heteroarylene of C3-C15, wherein the substituent group represented by the substituent group comprises at least one of deuterium, cyano, methyl and phenyl;
said L1、L2Independently selected from a single bond or one of the groups shown below,
Figure FDA0003144721800000022
the T is the same or different and is selected from C (R)m) Said R ismOne selected from hydrogen, deuterium, cyano, methyl and phenyl;
said L0The same or different one selected from single bond, substituted or unsubstituted phenylene, the substituent group represented by the above "substituted" includes at least one of deuterium, cyano, methyl, phenyl.
2. The heterocyclic derivative according to claim 1, wherein L isx、LyIndependently selected from one of a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted dibenzofuranyl and substituted or unsubstituted dibenzothiophenyl, wherein the substituent represented by the above "substitution" comprises at least one of deuterium, cyano, methyl and phenyl;
said L1、L2Independently selected from a single bond or one of the groups shown below,
Figure FDA0003144721800000023
the T is the same or different and is selected from C (R)m) Said R ismOne selected from hydrogen, deuterium and cyano;
said L0The same or different one selected from single bond, substituted or unsubstituted phenylene, and the substituent group represented by the above "substituted" includes at least one of deuterium and cyano.
3. The heterocyclic derivative according to claim 1, wherein L is1、L2Independently selected from a single bond or one of the groups shown below,
Figure FDA0003144721800000031
4. a heterocyclic derivative characterized in that the heterocyclic derivative is selected from one of the structures shown in the following,
Figure FDA0003144721800000032
Figure FDA0003144721800000041
Figure FDA0003144721800000051
Figure FDA0003144721800000061
Figure FDA0003144721800000071
Figure FDA0003144721800000081
Figure FDA0003144721800000091
Figure FDA0003144721800000101
Figure FDA0003144721800000111
5. an organic electroluminescent element comprising an anode, an organic layer, and a cathode, wherein the organic layer is disposed between the anode and the cathode, and the organic layer comprises an electron transport region containing the heterocyclic derivative according to any one of claims 1 to 4.
6. The organic electroluminescent device according to claim 5, wherein the organic layer further comprises a hole transport region containing a triarylamine compound represented by formula II,
Figure FDA0003144721800000112
wherein A, B is independently selected from one of the following substituents:
Figure FDA0003144721800000113
wherein, R isaOne of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or two adjacent groups are connected to form a ring;
the R isbOne of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or two adjacent groups are connected to form a ring;
said LaOne selected from single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C3-C30;
a is selected from 0,1, 2,3 or 4, b is selected from 0,1, 2,3, 4 or 5;
c is selected from one of the following groups:
Figure FDA0003144721800000121
wherein, R is12One selected from methyl, ethyl, propyl, butyl, phenyl, tolyl, biphenyl and naphthyl;
the R is13One selected from deuterium, methyl, ethyl, propyl, butyl, cyclohexyl, adamantyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, acridinyl, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, pyrenyl, indolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl;
said LbSelected from the group consisting of a single bond, phenylene, deuterated phenyl, deuterated naphthyl, tolylene, phenyleneOne of biphenyl, naphthylene, terphenylene, dibenzofuranylene, fluorenylene and dibenzothiophenylene;
c is selected from 0,1, 2,3, 4 or 5; d is selected from 0,1, 2,3 or 4; e is selected from 0,1, 2,3, 4,5, 6 or 7; f is selected from 0,1, 2,3, 4,5, 6, 7, 8 or 9.
7. The organic electroluminescent device according to claim 6, wherein C is selected from one of the following groups:
Figure FDA0003144721800000122
Figure FDA0003144721800000131
8. an organic electroluminescent device according to claim 6, wherein R isaIndependently selected from one of hydrogen, deuterium, methyl, ethyl, propyl, butyl, adamantyl, camphanyl, norbornyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, acridine, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, pyrenyl, indolyl, benzothienyl, benzofuranyl, dibenzothienyl and dibenzofuranyl, or adjacent two groups are connected to form a ring;
said LaOne selected from the group consisting of a single bond, phenylene, tolylene, biphenylene, naphthylene, terphenylene, dibenzofuranylene, fluorenylene, dibenzothiophenylene;
the R isbThe same or different groups are selected from one of hydrogen, deuterium, methyl, ethyl, propyl, butyl, adamantyl, camphanyl, norbornyl, phenyl, tolyl, biphenyl and terphenyl, or adjacent groups are connected to form a ring.
9. The organic electroluminescent device according to claim 6, wherein the triarylamine compound represented by formula II is selected from one of the following structures,
Figure FDA0003144721800000141
Figure FDA0003144721800000151
Figure FDA0003144721800000161
Figure FDA0003144721800000171
Figure FDA0003144721800000181
Figure FDA0003144721800000191
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